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Fuel Cells

for a Sustainable Energy Future


Sossina M. Haile
Materials Science / Chemical Engineering
California Institute of Technology

Graduate Students: Peter Babilo, William Chueh, Lisa Cowan, Mary


Louie, Justin Ho, Wei Lai, Mikhail Kislitsyn, Kenji Sasaki, Ayako Ikeda
Former Participants: Dane Boysen, Calum Chisholm, Tetsuya Uda,
Zongping Shao, Mary Thundathil
Funding: National Science Foundation, Department of Energy, Office
of Naval Research, (past: Kirsch Foundation, Powell Foundation)
Contents

• The Problem of Energy


– Growing consumption
– Consequences
– Sustainable energy resources
• Fuel Cell Technology Overview
– Principle of operation
– Types of fuel cells and their characteristics
• Recent (Caltech) Advances
– Too many to cover…

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The Problem of Energy

• The Problem
– Diminishing supply?
– Resources in unfriendly locations?
– Environmental damage?
• The Solution
– Adequate domestic supply
– Environmentally benign
– Conveniently transported
– Conveniently used

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World Energy Consumption

(annual) Source: US Energy Information Agency


264 8.4

Equivalent Power (TW, 1012)


211 6.7

Exa Joules (1018)


158 5.0

106 3.3

52 1.7

0 0

1999 totals: 400 Q-Btu, 422 EJ, 13TW


90% fossil
2020 projections: 630 Q-Btu, 665 EJ, 21TW
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Fossil Fuel Supplies
Source: US Energy Information Agency

2.0E+05
Rsv = Reserves (90%)
Rsc = Resources (50%)
1.5E+05
(Exa)J

1.0E+05
Unconv
Conv
5.0E+04

0.0E+00
Oil Oil Gas Gas Coal Coal
Rsv Rsc Rsv Rsc Rsv Rsc
Source Reserves, yrs Resources, yrs Total, yrs

Oil 13 - 20 10 – 35 23 - 55

Gas 11 - 25 7 – 40 18 - 65  400 yrs


Coal 32 270 300

56-77 287-345
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US Energy Imports/Exports: 1949-2004
Source: US Energy Information Agency

35
Imports Exports
6
30 Total
5
25

Quad BTU
Total 4
Quad BTU

20 Coal
3
15
10 2
Petroleum
5 1 Petroleum
0 0
1950 1960 1970 1980 1990 2000 1950 1960 1970 1980 1990 2000

35 Net • 65% of known petroleum reserves in Middle East


• 3% of reserves in USA, but 25% of world consumption
30
25
Quad BTU

20
15 1957: Net Importer
10
5
0

1950 1960 1970 1980 1990 2000

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Environmental Outlook
Global CO2 levels
340
2004: 378 ppm
atmospheric CO2 [ppm]

330
Projections:
320 500-700 ppm by 2020

310
• Anthropogenic Industrial
300 – Fossil fuel (75%) Revolution
– Land use (25%)
290

280

270
1000 1200 1400 1600 1800 2000
Source: Oak Ridge National Laboratory year
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Environmental Outlook

CO2 CH4 CO2 in 2004: 378 ppmv


(ppmv) (ppmv)
800
325 -- CO2 +4
-- CH4

T relative to
300 700

present (°C)
-- T 0
275
600
250
500 -4
225

200 400 -8

175 300
400 300 200 100 0
Thousands of years before present (Ky BP)

Intergovernmental Panel on Climate Change, 2001; http://www.ipcc.ch


N. Oreskes, Science 306, 1686, 2004; D. A. Stainforth et al, Nature 433, 403, 2005

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Energy Outlook

Supply Environmental Impact


• Fossil energy sufficient • Target
for world demand into – Stabilize CO2 at 550 ppm
the forseeable future – By 2050
• High geopolitical risk • Requires
– 20 TW carbon-free power
• Rising costs
– One 1-GW power plant
daily from now until then

Urgency
• Transport of CO2 or heat into deep oceans:
– 400-1000 years; CO2 build-up is cummulative
• Must make dramatic changes within next few years

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The Energy Solution

Solar The need:


1.2 x 10 TW at Earth surface
5
~ 20 TW by 2050
600 TW practical

Wind Biomass
2-4 TW extractable 5-7 TW gross
all cultivatable
land not used
Tide/Ocean for food
Currents
2 TW gross
Hydroelectric
Geothermal 4.6 TW gross
12 TW gross over land 1.6 TW technically feasible
small fraction recoverable 0.9 TW economically feasible
0.6 TW installed capacity
Nuclear
Waste disposal Fossil with sequestration
1% / yr leakage -> lost in 100 yrs

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The Energy Solution

• Sufficient Domestic Supply


– Coal, Nuclear, Solar
• Environmentally Sustainable Supply
– Solar (Nuclear?)
• Suitable Carrier
– Electricity? Hydrogen? Hydrocarbon?
• Challenges
– Convert solar (nuclear) to convenient chemical form
– Efficient consumption of chemical fuel

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A Sustainable Energy Cycle
H2O, CO2
C-free Source

Solar or nuclear
Capture e- power plants
H2

???

Batteries Hydrides?
Storage Hydrocarbon Liquid H2?

Delivery

e-
Utilization H2O + CO2
Fuel cell
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A Few Words on Hydrogen Fuel Cells

• Hydrogen energy density


– High energy content per unit mass of hydrogen
– But best storage technologies are at ~ 5 wt% H2
– 5x the weight of gasoline (for same energy content)
• Conventional hydrogen fuel cells require Pt
– DOE target: 1 g/kW (0.75 g/hp)
– 100 hp engine  75g Pt  $3,169
– 93% of US Pt is imported
– 80% of world reserves in one mine complex in SA
• Another 15% in one mine complex in Russia
– Converting US autos would double world consumption
– 4 yr auto lifetime, 20% recycling  out in 40 yrs

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Fuel Cells: Part of the Solution?

• High efficiency
automotive engine: 50-75 kW – low CO2 emissions
80
• Size independent
efficiency [%]

60
* • Various applications
40 – stationary
– automotive
20 – portable electronics
• Controlled reactions
0
0 5 10 15 20 25 – “Zero Emissions”
power plant size [MW] • Operable on hydrogen
– (if suitably produced)

*Can be as high as 80-90% with co-generation

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Fuel Cell: Principle of Operation
best of batteries, conversion device,
combustion engines not energy source
Anode Cathode

e-
H+
H2 O2
H2  2H+ + 2e- ½ O2 + 2H+ + 2e-  H2O

Electrolyte

Overall: H2 + ½ O2  H2O
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Fuel Cell Performance

H2 + ½ O2  H2O
1.2 0.8
1.17 Volts (@ no current) cross-over theoretical voltage
1.0
slow reaction kinetics
0.6
• voltage losses

Power [W / cm2]
0.8 peak power

Voltage [V]
– fuel cross-over
0.6 0.4
– reaction kinetics
– electrolyte resistance 0.4 electrolyte
resistance 0.2
– slow mass diffusion 0.2
slow mass
• power = I*V diffusion
0.0 0.0
• peak efficiency at low I 0.0 0.4 0.8 1.2 1.6
Current [A / cm2 ]
• peak power at mid I

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Fuel Cell Components

• Components electrodes catalyst

– Electrolyte (Membrane)
• Transport ions
• Block electrons, gases
– Electrodes
• Catalyze reactions
• Transport
– Ions, electrons, gases
• May be a composite sealant
– (electro)Catalyst + electrolyte
– Conductors +
– Pore former Membrane-Electrode
Assembly (MEA)
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Fuel Cell Types

Types differentiated by electrolyte, temperature of operation

Low T  H2 or MeOH; High T  higher hydrocarbons (HC)


Efficiency tends to  as T , due to faster electrocatalysis

Type PEM AFC PAFC MCFC SOFC


°C 90-110 100-250 150-220 500-700 700-1000
[°F] [200-230] [212-500] [300-430] [930-1300] [1300-1800]

Fuel H2 + H2O H2 H2 HC + CO HC + CO

Electrolyte Nafion KOH H3PO4 Na2CO3 Y-ZrO2


Ion H3O+  OH-  H+  CO32-  O2- 

Oxidant O2 O2 + H2O O2 O2 + CO2 O2

By-products: H2O, CO2

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Fuel Cell Choices

Temperature sets operational parameters & fuel choice

• Ambient Temperature • High Temperature


 Rapid start-up  Fuel flexible
 H2 or CH3OH as fuels  Very high efficiencies
 Catalysts easily poisoned  Long start-up

• Applications • Applications
– Portable power – Stationary power
– Many on/off cycles – Auxiliary power in
– Small size portable systems

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Technology Status

• Many, many demonstrate sites and vehicles


– Stationary PAFC (200 kW) at military sites since 1995
– Stationary SOFC (100 kW) operated for 20,000 hrs
– Toyota and Honda PEM FC vehicles released 2002
– DaimlerChrysler, Ford and GM, 2005; Hyundai planned
• Legislation is a key driver
– California zero emissions automotive standards
– China set for tough ‘CAFE’ standards
• Cost is a major barrier
– Precious metal catalysts, fabrication, complexity
• Uncertainty in future fuel infrastructure
– Gasoline for how long? Hydrogen? Methanol?

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Fuel Cell System Complexity

Membrane electrode assembly


sealant
electrolyte

electrodes catalyst
Electrolyte

System
Stack

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Philosophy

Challenge
• Limitation of fuel cell materials places severe
design constraints on fuel cell systems
Approach
• Material modification for improved performance
and system simplification
• New materials discovery for next generation
fuel cell systems
• Novel system designs

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Fuel Cell Innovations

• New Electrolytes
– Intermediate temperature operation
• Lower the temperature below solid oxide fuel cells
• Raise the temperature above polymer fuel cells

• New Catalysts
– Enhance reaction kinetics (improve efficiency)
– Reduce susceptibility to poisons (reduce complexity)
• Novel integrated designs
– Dramatically improve thermal management
– Utilize micromachining technologies – micro fuel cells

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New Electrolytes: Solid Acids
NSF & DOE Sponsored Program
(past ONR support)
“PEM” Fuel Cells
Proton Exchange Membrane or Polymer Electrolyte Membrane

H(H2O)n+
Nafion (Dupont)
H2O
• saturate with H2O
 SO3- + (H2O)nH+
– inverse micelle structure
1 nm
• H(H2O)n+ ion transport 

(CF2)n 
 High conductivity
 Flexible, high strength
 Requires humidification &
water management
 Operation below 90°C
 Permeable to methanol
Kreuer, J Membr Sci 2 (2001) 185.

Target: 120-300°C; examine inorganic H+ conductors

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Solid Acids

• Chemical intermediates
between normal salts and d is o r d e r e d
normal acids: “acid salts” s tru c tu re p o ly m e r

lo g ( c o n d u c t iv it y )
½(Cs2SO4) + ½(H2SO4)  CsHSO4

• Physically similar to salts


• Structural disorder at
‘warm’ temperatures n o rm a l
• Properties
s tru c tu re
 Direct H+ transport s tru c tu ra l 
 Humidity insensitive t r a n s it io n
 Impermeable T 1 /T
 Water soluble!! Brittle

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Proton Transport Mechanism

H
Sulfate group
reorientation
S

O 10-11 seconds

Proton transfer

10-9 seconds

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Conductivity of Solid Acids

• CsHSO4 [Baranov, 1982] 250°C 150°C 100°C 50°C 25°C


-1
• CsHSeO4 [Baranov, 1982] Superprotonic
-2 transition

log(conductivity) [S / cm]
• (NH4)3H(SO4)2
[Ramasastry, 1981] -3

• Rb3H(SeO4)2
-4
[Pawlowski, 1988]

• Cs2(HSO4)(H2PO4) -5

[Chisholm & Haile, 2000]


-6
• -Cs3(HSO4)2(H2PO4)
[Haile et al., 1997] -7

• K3H(SO4)2 -8
[Chisholm & Haile, 2001] 2.00 2.25 2.50 2.75 3.00 3.25
-1
1000/T K

But sulfates and selenates are unstable under reducing conditions…


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Solid Acid Properties

The Good The Bad


• H+ transport only • Known compounds are
– No electro-osmotic drag water soluble
– No electron transport – Operate at T  100ºC
– Alcohol impermeable – Insoluble analogs?

• Humidity insensitive • Few are chemically stable


conductivity The Ugly
• Stable to ~ 250ºC • Poor processability and
• Inexpensive mechanical properties
• Chemically non-aggressive – Composite membranes
with inert polymers

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CsH2PO4 as a Fuel Cell Electrolyte

• Expected to have chemical stability


– 3CsH2PO4 + 11H2  Cs3PO4 + 3H3P + 8H2O
– dG(rxn) >> 0

• But does it have high conductivity?


• Does it have sufficient thermal stability?
• Literature dispute
– High conductivity on heating due to H2O loss
– High conductivity due to transition to a cubic phase

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CsH2PO4 Dehydration

CsH2PO4  CsPO3 + H2O


pressure detector
Tc = 230 Toper = 250°C
0.4 77

Water temperature ( C)
Equilibrium pH O(atm)
CsH2PO4 + H2O

o
0.3 P(H2O) operation
71

4
PO
0.2

4-x
62

PO
2
H
Cs

x
0.1

2-2
47

H
Cs
0.0
200 225 250 275 300

Temperature(C)

Use water partial pressure to suppress dehydration

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Conductivity of CsH2PO4
o
Temperature [ C]
260 240 220 200 180 160

0.42 eV 1st heating


-2 1st cooling
log(conductivity) [ cm ]

2nd heating
-1

2nd cooling
-1

Humidified air
p[H2O] = 0.4 atm
-4

-6 230 °C

1.9 2.0 2.1 2.2 2.3 2.4


-1
1000/T [K ]
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Proof of Principle

H2O, H2 | Cell | O2, H2O


T = 235ºC 50 mW/cm2
60
1.0 before

Power density (mW cm )


-2
after 50
0.8 Compared to polymers
Cell voltage (V)

40
power  High open circuit voltage
0.6
30
– Theoretical: 1.15V
0.4 20 – Measured: 1.00 V
voltage – Polymers: 0.8-0.9 V
0.2 10
 Power density
0.0 0
– Polymers: > 1 W/cm2
0 50 100 150 200 250 300
Current density (mA cm )
-2 • Platinum content
– Polymers: ~ 0.1 mg/cm2
260m membrane; 18 mg Pt/cm2

D. A. Boysen, T. Uda, C. R.I. Chisholm and S. M. Haile, Science 303, 68-70


(2004)

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Fuel Cell Longevity: Stable Performance

Cell voltage (V) 1.0 H2, H2O | cell | O2, H2O

0.8 260 m thick CsH2PO4 electrolyte


T = 235ºC
0.6 Current = 100 mA/cm2

0.4
2
on, 100 mA/cm off
0.2

0.0
0 20 40 60 80 100

Time (h)

• CsH2PO4 – no degradation in 110 hr measurement


• CsHSO4 – functions for only ~ 30 mins (recoverable degradation)
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3rd Generation Fuel Cell
Fine CsH2PO4 H2, H2O | cell | O2, H2O

T = 248°C
8 mg Pt/cm2

2 m

Slurry deposit

T. Uda & S.M. Haile, Electrochem &


10-40 m pores, ~40% porosity Solid State Lett. 8 (2005) A245-A246

Open circuit voltage: 0.9-1.0 V Peak power density: 285-415 mW/cm2

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Impact
S. M. Haile, D. A. Boysen, C. R. I. Chisholm and R. B. Merle,
“Solid Acids as Fuel Cell Electrolytes,” Nature 410, 910-913 (2001).

The promise of protonics Solid Acids Show Promise...


Some Like It Medium Hot

Nature: News & Views Physics Today Online


Science Now Magazine
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Fuel Cell Stack

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‘Direct’ Alcohol Fuel Cells

Methanol in proton exchange membrane fuel cells


CH3OH + H2O  6H+ + CO2 + 6e-
CH3OH + H2O  3H2 + CO2

• SAFCS ideal thermal match


– Reforming rxn: 200 – 300°C
– Electrolyte: 240 – 280°C
– Steam reforming: endothermic
– Fuel cell rxns: exothermic

• Integrated design
– Incorporate alcohol reforming
catalyst in anode chamber

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‘Direct’ Methanol Fuel Cells
With reformer Without reformer
T = 260 °C; 47 m membrane T = 240 °C; 34 m membrane
1.0 0.4

Power density (W /cm )


2
hydrogen
Cell voltage (V)

0.8
hydrogen 0.3
0.6 reformate
1%CO
24%CO2 0.2
0.4 methanol
42 vol%
0.1
0.2
methanol
0.0 0.0
0.0 0.5 1.0 1.50.0
1.5 0.5 1.0 1.5
2
Current density (A/cm )
• Methanol power ~ 85% H2 power • Reformate power ~ 90% H2 power
• For polymer fuel cells ~ 10% • Methanol power ~ 45% H2 power

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‘Direct’ Alcohol Fuel Cells

With reformer
T = 260 °C; 47 m membrane

ethanol
36 vol%
Vodka
80 proof

• Ethanol power ~ 40% H2 power

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New Cathodes
for Solid Oxide Fuel Cells
NSF & DOE Sponsored Program
(past DARPA support)
State-of-the-Art SOFCs

Component Materials
cathode (air electrode) (La,Sr)MnO3

electrolyte Zr0.92Y0.08O2.96 = yttria stabilized zirconia (YSZ)

Ni + YSZ composite
anode (fuel electrode)

• Operation: ~1000 °C • Goal: 500 – 800 °C


• Fuel flexible, efficient • Challenges
• But… – Slower kinetics 
– All high temp materials – Electrolyte resistance
– Costly (manufacture) – Poor anode activity
– Poor thermal cyclability – Poor cathode activity

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Solid Oxide Fuel Cell Cathodes

(Ba0.5Sr0.5)(Co0.8Fe0.2)O2.3
• Traditional cathodes
– A3+B3+O3 perovskites
– Poor O2- transport
– Limited reaction sites
almost
• Our approach 1 in 4 vacant
– High O2- flux materials
– Extended reaction sites
– A2+B4+O3 perovskites

‘triple-point’ path electrode bulk path


O2 O2
Oad
Oad cathode 2e-
Oad 2e- O2-
cathode

O2- O2-
electrolyte electrolyte

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Cathode Electrocatalysis

½ O2 +
2e -

O2,
• Symmetric cell Ar, O= Electrolyte
cathode
layers
resistance (CO2)
measurements 2e-
Ag current ½ O2
-
collectors

+
• Equivalent circuit Rcathode
– Distinguish resistance
contributions using Relectrolyte
frequency dependent
measurements Rcathode
-

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Cathode Electrocatalysis
o O2 Oad
Temperature ( C)
slow 2e-

750 700 650 600 550 500 450 400 fast O2- cathode
.cm )
2

10 10 O2-
electrolyte
P(O2) = 0.21 atm
Cathode area specific resistance (

1 1 Ea same as oxygen surface


exchange (113 kJ.mol-1)
0.5 – 0.6 cm2
0.1 0.1 Bulk diffusion is fast
-1
Ea=116 kJ.mol (46 kJ.mol-1)

0.01 0.01 Other ‘advanced’ cathodes


Symmetric cell (2-electrode)
Half cell (3-electrode) (PrSm)CoO3: 5.5 cm2
1.0 1.1 1.2 1.3 1.4 1.5 (LaSr)(CoFe)O3: 48 cm2
-1
1000/T (K 

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Cell Fabrication
Anode supported Dual dry Sinter,
press 1350oC 5h
NiO + SDC SDC
(Ce0.85Sm0.15O2)
NiO + SDC 600oC 5h,
15%H2
Spray
Calcine, 950oC
cathode
cathode 5h, inert gas

electrolyte Porous
anode
anode

0.71 cm2
Anode: 700 m Electrolyte surface

~ 20m

1.3 cm
Electrolyte

Cathode: 20 m
2 m

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Fuel Cell Power Output
H2, 3% H2O | fuel cell | Air > 1 W/cm2 at 600°C!!!
1.0 o
600 C

Power density (mW.cm )


1000

-2
o
550 C
0.8 o
500 C
Voltage (Volts)

445 C 800
o

o
0.6 400 C
600

0.4
400

0.2 200

0.0 0
0 1000 2000 3000 4000
-2
Current density (mA.cm )
Comparison: literature cathode material  350 mW/cm2 at 600°C

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Impact
Z. Shao and S. M. Haile, “A High Performance
Cathode for the Next Generation Solid-Oxide
Cooler Material Boosts Fuel Cells Fuel Cells,” Nature 431, 170-173 (2004).

SOFC cathode is hot stuff…


Next generation of fuel cells…

Tech Research News


R & D Focus
Towards a Sustainable Energy Future Fuel Cell Works
Summary & Conclusions

• Sustainable energy is the ‘grand challenge’ of


the 21st century
– Solutions must meet the need, not the hype
– Fuel cells can play an important role
• Solid acid fuel cells
– Radical alternatives to state-of-the-art
– Viability demonstrated; spin-off company established
• Solid oxide fuel cells
– Promising alternative cathode discovered
• Still plenty of need for fundamental research

“The stone age didn’t end because we ran out of stones.”


-Anonymous
Towards a Sustainable Energy Future
Acknowledgments

• The people Zongping

Mary
Tetsuya

Justin

Wei

Calum Dane

Kenji

• The agencies
– National Science Foundation, Office of Naval Research,
DARPA, California Energy Commission, Department of
Energy, Kirsch Foundation, Powell Foundation

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Selected Relevant Publications

• T. Uda, D. A. Boysen, C. R. I. Chisholm and S. M. Haile, “Alcohol Fuel Cells at


Optimal Temperatures,” Electrochem. Solid State Lett. 9, A261-A264 (2006).
• T. Uda and S. M. Haile, “Thin-Membrane Solid-Acid Fuel Cell,” Electrochem. Solid
State Lett. 8, A245-A246 (2005).
• D. A. Boysen, T. Uda, C. R.I. Chisholm and S. M. Haile, “High performance Solid
Acid Fuel Cells through humidity stabilization,” Science Online Express, Nov 20,
2003; Science 303, 68-70 (2004).
• D. A. Boysen, S. M. Haile, H. Lui and R. A. Secco “High-temperature Behavior of
CsH2PO4 under both Ambient and High Pressure Conditions,” Chem. Mat. 15, 727-
736 (2003).
• R. B. Merle, C. R. I. Chisholm, D. A. Boysen and S. M. Haile, “Instability of Sulfate
and Selenate Solid Acids in Fuel Cell Environments,” Energy and Fuels 17, 210-
215 (2003).
• S. M. Haile, D. A. Boysen, C. R. I. Chisholm and R. B. Merle, “Solid Acids as Fuel
Cell Electrolytes,” Nature 410, 910-913 (2001).

• Z. P. Shao, S. M. Haile, J. M. Ahn, P.D. Ronney, Z. L. Zhan and S. A. Barnett, “A


thermally self-sustained micro Solid-Oxide Fuel Cell stack with high power
density,” Nature 435, 795-798 (2005).
• Z. Shao and S. M. Haile, “A High Performance Cathode for the Next Generation
Solid-Oxide Fuel Cells,” Nature 431, 170-173 (2004).

• S. M. Haile, “Fuel Cell Materials and Components,” (invited) Acta. Met. 51, 5981-
6000 (2003).
• S. M. Haile, “Materials for Fuel Cells,” (invited) Materials Today 18, 24-29 (2003).

Towards a Sustainable Energy Future

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